CN105518068A - Ionic strength triggered disintegration of films and particulates - Google Patents

Ionic strength triggered disintegration of films and particulates Download PDF

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Publication number
CN105518068A
CN105518068A CN201480049285.6A CN201480049285A CN105518068A CN 105518068 A CN105518068 A CN 105518068A CN 201480049285 A CN201480049285 A CN 201480049285A CN 105518068 A CN105518068 A CN 105518068A
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methyl
composition
ionic strength
arbitrary
plate
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CN105518068B (en
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S·巴克尔
A·S·卡里卡利
P·梅尔坎多
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Rohm and Haas Co
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Bayer Technology Services GmbH
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015Biocides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • C08L23/0876Neutralised polymers, i.e. ionomers
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04Homopolymers or copolymers of ethene
    • C09D123/08Copolymers of ethene
    • C09D123/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0869Acids or derivatives thereof
    • C09D123/0876Neutralised polymers, i.e. ionomers
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance
    • C09D5/1668Vinyl-type polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2248Oxides; Hydroxides of metals of copper

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Abstract

A composition comprising an ethylene (meth)acrylic acid copolymer and an anti- fouling agent is provided. The composition selectively disintegrates in media of different ionic strengths. Also provided is a method of preventing fouling using the composition.

Description

The disintegration that the ionic strength of film and particle triggers
the cross reference of related application
This application claims the U.S. Provisional Application the 61/883rd submitted on September 27th, 2013, the right of priority of No. 618, the mode that described application is quoted in full is incorporated herein.
Technical field
The present invention relates to the composition of selectivity disintegration in the medium of different ionic strength.
Background technology
Exist and wherein protect material in high ionic strength system or surface by favourable multiple situation.For example, in family's nursing market, brand-owner has moved to more concentrated delivery system, as efficient concentration scouring agent and unit dose products.In these cases, the product sold is compared with during use, and ionic strength is significantly higher.Another field that composition is exposed to high ionic strength medium is in coating for watercraft.Therefore, need to be not dissolved in the composition in high ionic strength medium.
Summary of the invention
In an aspect, provide a kind of composition, it comprises ethene (methyl) acrylic copolymer, and the carboxylic acid group at least partially wherein in (methyl) acrylate component is through neutralization; And plate-out agent.
In one aspect of the method, a kind of film composition is provided, it comprises ethene (methyl) acrylic copolymer and plate-out agent, carboxylic acid group at least partially wherein in (methyl) acrylate component through neutralization, and wherein the ratio of ethylene component and (methyl) acrylate component about about between 50: 50 to 90: 10.
In one aspect of the method, provide a kind of through coated obj ect, it comprises object; Comprise the coating composition of ethene (methyl) acrylic copolymer, the carboxylic acid group at least partially wherein in (methyl) acrylate component is through neutralization; And plate-out agent.Coating composition not disintegration in high ionic strength medium, and disintegration in low ionic strength media.
Embodiment
The present invention relates to the chemical composition of ethene (methyl) acrylic copolymer.As used herein, term " composition " can mean such as mixture, solution or dispersion liquid.As used herein, " (methyl) vinylformic acid " means vinylformic acid, methacrylic acid or its mixture.Ethene (methyl) vinylformic acid (EAA) multipolymer may be used in extensive multiple application, comprises high-performance tackiness agent, flexible film package, pouch and extrusion coated and extruded lamination application.The free acid form of ethene (methyl) acrylic copolymer can neutralize required degree with the alkali be applicable to.Depend on degree of neutralization, ethene (methyl) acrylic copolymer with faling apart property of different in moisture can be obtained.For example, when (methyl) acrylate moiety stoichiometric quantity alkali completely in and time obtain complete water dispersible or under certain conditions, completely water-soluble, but depend on its for application, part neutralization EAA multipolymer can be that water dispersible, water sensitive or water are insensitive.
Multipolymer may be used for various composition, such as liquid composition or film composition.This kind of film can also via grinding or alternate manner physically reduced in size with provide there is large surface area be encapsulated activeconstituents.Similarly, sizing particle can also by method known in affiliated field, as spraying dry and freeze-drying cause liquid composition produce.Composition can comprise copolymer compositions maybe can comprise composition with one or more additional material to provide application specificity physical property (tensile strength, weather resistance, tackiness etc.).Additional material can comprise linking agent, fluidizer, disintegrating agent and/or tensio-active agent.
Linking agent can comprise such as Ca 2+, Mg 2+, Al 3+or Zn 2+.Except linking agent, composition can comprise at least one additional additive, as fluidizer, disintegrating agent and/or tensio-active agent.Fluidizer can be hydrophobicity fluidizer, wetting ability fluidizer or its combination.For example, fluidizer can especially phenylcarbinol, lB-65 (the soluble lubricant of polyalkylene glycol (PAG) class synthetic water) or T-BEP (three (butoxyethyl group) phosphoric acid ester, alkyl phosphate film coalescence aid and fluidizer).Disintegrating agent can be such as vinylformic acid, PVOH, starch, Mierocrystalline cellulose or the second multipolymer.Tensio-active agent can be such as anion surfactant, nonionogenic tenside, amphoterics or its mixture.The example of anion surfactant comprises known those in affiliated field, as 2A1 (alkyl diphenyl base oxygen stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate), Texapon Special, Sodium Lauryl Sulphate BP/USP, sodium laureth sulfate.The example of nonionogenic tenside comprises known those in affiliated field, as polyoxyethylene glycol alkyl ether, polyoxypropylene diols alkyl oxide, glucoside alkyl oxide, polyoxyethylene glycol octyl phenol ether, polyoxyethylene glycol alkylbenzene phenolic ether, alkyl esters of glycerol, polyoxyethylene glycol sorbitan alkyl esters and sorbitan alkyl esters.The example of amphoterics comprises known those in affiliated field, as lO (lauryl amine oxide compound).
The not disintegration in the medium (such as caustic alkali, household bleach, seawater, synthetic sea water) that ionic strength is high of this composition.As used herein, term " disintegration " means dissolving, dispersion or solvable.Medium can be such as solution, slurries, dispersion liquid or paste form.Medium can also not contain quite a large amount of inorganic salt in fact, but medium can comprise organic amine salt to provide required ionic strength and basicity.The example of these organic amine salts comprise carboxylic acid and fatty acid ester through monosubstituted, two to replace or trisubstituted alkylamine salts.High ionic strength medium is that salinity is greater than about 3%, is more preferably greater than the medium of about 7%.After being exposed to low ionic strength aqueous medium (such as the washing liq of deionized water, standard tap water, washing machine), film will decompose in several minutes, under stirring gently, become dispersion in low ionic strength media.Low ionic strength media to be salinity be about 0 to about 2% medium (such as tap water, deionized water).
In marine vessel applications, as on canoe or ship, the salinity of seawater provides the ionic strength prevented required for composition dissolves or disintegration, therefore, composition can use the substrate of making coatings, and it after application, can after usage via fresh water, namely low ionic strength washing is removed.In addition, composition can make its mode containing the additive that can serve as plate-out agent prepare.
Biological fouling or biological incrustation are microorganisms, plant, algae or animal accumulate on wetted surface.Anti-incrustation is the technique removed or prevent these from accumulating.The example of plate-out agent includes, but is not limited to biocide, as organo-tin compound (such as tributyl tin part (TBT)) and copper compound (such as cupric oxide); With the coating based on organic polymer.Coating based on organic polymer can be hydrophobicity, as based on those of fluoropolymer and silicone; Or wetting ability, as based on high degree of hydration zwitterionic those (such as glycinebetaines and sultaine).
The present composition may be used in any application needing to prevent growth or incrustation, as in water tower, on dock, on metal dam assembly, on oil rig and on hull.
In a particular embodiment, composition can comprise ethene (methyl) acrylic copolymer and plate-out agent.Carboxylic acid group at least partially in (methyl) acrylate component neutralizes through alkali, produces salt.For example, carboxylic acid group can with sodium cation neutralization to form sodium salt.In another embodiment, carboxylic acid group can with potassium cationic neutralization to form sylvite.Degree of neutralization can about 70% and about between 100%, preferably about 90% and about between 100%, and more preferably about 98% and about between 100%.In other embodiments, degree of neutralization can about 70% and about between 95%, preferably about 85% and about between 95%, more preferably about 90% and about between 95%.A part in all the other (methyl) vinylformic acid or all can through ionomer.Increase degree of neutralization and increase the dispersiveness of composition in low ionic strength media.Those skilled in the art will realize that the appropriate method measuring degree of neutralization.See such as No. the 3rd, 472,825, United States Patent (USP).
Composition can also comprise water, can be coated on object or can be dry to produce the liquid composition of such as film or particle to make its formation.In certain embodiments, composition can comprise about 60 % by weight to about 80 % by weight water.Ethene (methyl) acrylic copolymer may reside in the dispersion liquid that the known multiple method of those skilled in the art can be formed.In multipolymer, ethene and (methyl) acrylic acid weight ratio can about 50: 50 and about between 90: 10, and preferably about 70: 30 and about between 90: 10, and more preferably about 75: 25 and about between 80: 20.
Composition may be used for producing coated obj ect, such as, be coated with ship, dock or dam.Coated obj ect can comprise object, the composition of (methyl) acrylic copolymer that comprises ethene and plate-out agent.
Also openly prevent the method for growth or incrustation.In these methods, the present composition to be coated on object and to prevent microorganism, plant, algae or animal from accumulating on article surface.
example
example 1
Functionalised polyolefin compositions for this example is the mixture of ethene (methyl) vinylformic acid (80 % by weight ethene and 20 % by weight (methyl) vinylformic acid) with potassium hydroxide neutralization.Degree of neutralization is 92%.Composition can use program preparation known in affiliated field.Openly apply for that No. WO2011034883 and PCT openly apply for No. WO2012082624 see such as No. 2011/0319521st, U.S. Patent application, PCT.The pH of composition is 10 and cloth network gram Field viscosity (Brookfieldviscosity) is 500 (Bu Luoke Field RVT, No. 2 axles, 20RPM, 25 DEG C) and hereinafter referred to as EAA-K.
1.3g cupric oxide suspension (in water 46%) is added in the composition (6.6g, 23% is active) of EAA-K.Stir material via manual shake flask to suspend completely in the composition to make copper particle.203 μm of (8 mil) drawdown rods are used to cast on glass by coating solution, in 40 degrees Celsius of baking ovens dry 1 hour subsequently.Film and it is shown as independent film is removed from glass.Five membrane samples (about 2cm × 2cm) are immersed in deionized water at room temperature, tap water, synthetic sea water, NaCl saturated solution and KCl saturated solution respectively.Be inverted bottle to realize stirring.
In high ionic strength system (synthetic sea water, NaCl saturated solution and KCl saturated solution), film seems to keep complete, and does not observe the colour-change of supernatant liquor.This shows the low-level leached at experimental session membrane component in water.In low ionic strength media (deionized water and tap water), film divided in five minutes, and observed that supernatant liquor becomes brown after making solid settlement.This shows the high level in the leaching of experimental session film.
Although describe the present invention according to a preferred embodiment of the invention above, can modify to it within the spirit and scope of the present invention.The application be therefore intended to contain use General Principle disclosed herein of the present invention any change, use or reorganization.In addition, the application's intention contains the practice of the known or convention belonging to the field that the present invention relates to and belongs to departing from of the present invention this type of in restriction of following claims.

Claims (15)

1. a composition, it comprises:
Ethene (methyl) acrylic copolymer, the carboxylic acid group at least partially wherein in (methyl) acrylate component is through neutralization; With
Plate-out agent.
2. composition according to claim 1, it comprises water further.
3. composition according to claim 1 and 2, wherein said ethene (methyl) acrylic copolymer is present in dispersion liquid.
4. the composition according to claim arbitrary in Claim 1-3, in wherein said multipolymer, ethene and (methyl) acrylic acid ratio are about between 50: 50 and 90: 10.
5. the composition according to claim arbitrary in claim 1 to 4, wherein degree of neutralization is about 70% and about between 100%.
6. the composition according to claim arbitrary in claim 1 to 5, it is included in about 60% and water about between 80%.
7. the composition according to claim arbitrary in claim 1 to 6, wherein said plate-out agent is cupric oxide.
8. the composition according to claim arbitrary in claim 1 to 6, wherein said plate-out agent is hydrophobic coating.
9. the composition according to claim arbitrary in claim 1 to 6, wherein said plate-out agent is hydrophilic coating.
10. a film composition, it comprises: ethene (methyl) acrylic copolymer and plate-out agent,
Carboxylic acid group at least partially wherein in (methyl) acrylate component through neutralization, and
Wherein the ratio of ethylene component and described (methyl) acrylate component is about about between 50: 50 and 90: 10.
11. film compositions according to claim 10, it comprises at least one additive further, and wherein said additive is fluidizer, linking agent, disintegrating agent and/or tensio-active agent.
12. film compositions according to claim 10 or 11, wherein degree of neutralization is about 70% and about between 100%.
13. film compositions according to claim arbitrary in claim 10 to 13, wherein said plate-out agent is selected from the group be made up of biocide, hydrophobic coating and hydrophilic coating.
14. 1 kinds of coated obj ect, it comprises:
Object;
Comprise the coating composition of ethene (methyl) acrylic copolymer, the carboxylic acid group at least partially wherein in (methyl) acrylate component is through neutralization; And plate-out agent,
The not disintegration in high ionic strength medium of wherein said coating composition, and
The disintegration in low ionic strength media of wherein said coating composition.
15. coated obj ect according to claim 14, wherein said high ionic strength medium is seawater and described low ionic strength media is fresh water.
CN201480049285.6A 2013-09-27 2014-09-25 The disintegration of the ionic strength of film and particle triggering Expired - Fee Related CN105518068B (en)

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US201361883618P 2013-09-27 2013-09-27
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